Process for light-induced curing of epoxy resins in presence of cyclopentadienylmanganese tricarbonyl compounds

ABSTRACT

The cure of polyepoxide resins with a reactive acid anhydride or polymercaptan curing agent is accelerated in the presence of light and a catalytic amount of a cyclopentadienyl-manganese tricarbonyl compound, e.g., methylcyclopentadienyl-manganese tricarbonyl.

O United States Patent [1 1 [111 3,709,861 Anderson [451 Jan. 9, 1973 {54] PROCESS FOR LIGHT-INDUCED [58] Fleld of Search...260/47 EC, 2 EC, 78.4 EP, 59, CURING OF EPOXY RESINS IN 260/77.5 NC, 429 R; 252/431 PRESENCE OF CYCLOPENTADIENYLMANGANESE [56] References Cited TRICARBONYL COMPOUNDS UNITED STATES PATENTS [75] Inventor: William S. Anderson, Oakland,

Calif 3,497,488 2/ I970 Dawans et al ..252/43l R [73] Assignee: Shell Oil Company,l-louston,Tex. Primary Examiner wimam H. Short Assistant Examiner-T. Pertilla 22 F1 d: D .14 1970 :2]; A N 9:180 Attorney-Raymond Owyang and Martin S. Baer [57] ABSTRACT [52] Cl "260/47 C 101/471 106/163 The cure of polyepoxide resins with a reactive acid an- 7 1 43 1 hydride or polymercaptan curing agent is accelerated 1 39 4 EP in the presence of light and a catalytic amount of a EP 560/47 EA 260/59 5 NC cyclopentadienyl-manganese tricarbonyl compound, 260,78 EP 2 60/741 260/4 7 e.g., methylcyclopentadienyl-manganese tricarbonyl 260/429 R, 260/830 R, 260/830 P, 226245383356 3 Claims, No Drawings 51 lntQCl. ..C08g 30/12 PROCESS FOR LIGHT-INDUCED CURING OF EPOXY RESINS IN PRESENCE OF CYCLOPENTADIENYLMANGANESE TRICARBONYL COMPOUNDS BACKGROUND OF THE INVENTION l. Field of the Invention A polyepoxide resin is defined as any molecule containing more than one vie-epoxy group capable of being converted to a useful thermoset form. The con version is accomplished by the addition of a chemically active compound known as a curing agent. Some curing agents promote curing by catalytic action, i.e., promote the polymerization of the polyepoxide resin to a homopolymer (one composed essentially of epoxyresin molecules linked together through their own reactive sites). Other curing agents participate directly in the reaction and are chemically bound into the resin chain to produce a heteropolymer (one composed essentially of polyepoxide resin molecules linked together through the reactive sites of the curing agent). The present invention is directed to the preparation of heteropolymers of polyepoxide resins and reactive acid anhydride or polymercaptan curing agents.

2. Description of the Prior Art Strohmeier et al, Z. Naturforsch, 21 b, 1 1 l9 (l966), disclose the polymerization of monoepoxides such as propylene oxide by ultraviolet irradiation in the presence of manganese carbonyls such as manganese decacarbonyl and cyclopentadienylmanganese tricarbonyl. However, this light-induced polymerization is conducted at elevated temperatures and in the absence of oxygen-containing gases such as air. The necessity of conducting the polymerization in the absence of air and at elevated temperatures severly limits its utility, par ticularly for surface coatings.

Light-sensitive catalysts for epoxy resin cures such as benzenediazonium fluoborates (US. Pat. No. 3,205, l 57) and N-nitroso-alpha,beta-unsaturated amines (U.S Pat. No. 3,074,869), which are not subject to inhibition by free-radical inhibitors such as oxygen, are known. However, such photocatalysts are expensive and suffer from short pot lives, i.e., they catalyze epoxy cures even in the absence oflight.

SUMMARY OF THE INVENTION It has been found that cyclopentadienylmanganese tricarbonyl compounds serve as photocatalysts for the cure of polyepoxide resins with acid anhydride or polymercaptan curing agents. For example, a mixture of diglycidyl polyether of Bisphenol A and a polymercaptan curing agent additionally containing a minor amount of methylcyclopentadienylmanganese tricarbonyl is cured in less than l hours at room temperature after exposure to light, but yet has a pot life in the dark of several weeks.

DESCRIPTION OF PREFERRED EMBODIMENTS Generically, the photocatalyst comprises cyclopentadienylmanganese tricarbonyl compounds represented by the formula I wherein R is a simple or substituted cyclopentadienyl radical containing from five to about 24 carbon atoms, preferably from five to 10 carbon atoms.

photocatalyst is methylcyclopentadienylmanaganese tricarbonyl.

The photocatalysts of the process of the invention are employed for the cure of polyepoxide resins with acid anhydride or polymercaptan curing agents.

The polyepoxide resins used in preparing the curable compositions'of' the present invention comprise those organic materials which have more than one vic-epoxy group, i.e., a

group, which group may in a terminal position, i.e., a /0 H- -CCH group, or in an internal position, i.e., a

group. The polyepoxides may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted with substituents, such as chlorine, hydroxyl groups, ether radicals, and the like.

Examples of such polyepoxides include, among others, I

l,4-bis(2,3-epoxypropoxy)benzene l ,3-bis( 2,3-epoxypropoxy)benzene 4,4'-bis( 2,3-epoxypropoxy)diphenyl ether 1 ,8-bis( 2, 3 -epoxypropoxy )octane l,4-bis(2,3-epoxypropoxy)cyclohexane 4,4-bis(2-hydroxy-3,4-epoxybutoxy)diphenyl dimethylmethane l ,3-bis(4,5-epoxypent0xy )-5-chlorobenzene l ,4-bis( 3 ,4-epoxybutoxy )-2-chlorocyclohexane 1 ,3-bis( 2-hydroxy-3,4-epoxybutoxy)benzene l ,4-bis( 2-hydroxy-4,5-epoxypentoxy )benzene.

Other examples include the epoxy polyethers of polyhydric phenol. Polyhydric phenols that can be used for this purpose include, among others, resorcinol, catechol, hydroquinonc, methyl resorcinol, or polynuclear phenols, such as 2,2-bis(4-hydroxyphenyl)propanc (Bisphenol A), 2,2-bis(4-hydroxyphenyl) butane, 4,4-dihydroxybenzophenone, bis(4-hydroxyphenyl)ethane, 2,2-bis (4-hydroxyphenyl)pentane, 1,5-dihydroxynaphthalene and phenolformaldehyde novolaks (phenol groups attached through methylene bridges).

Another group of polyepoxides comprises the polyepoxypolyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as hydrofluoric acid, or of the halogen-containing epoxides, such as epichlorohydrin, with a polyhydric alcohol, and subsequently treating the resulting product with an alkaline component. As used herein and in the claims, the expressions polyhydric alcohol is meant to includethose compounds having at least two free alcoholic OH groups and includes the polyhydric alcohols and their ethers and esters, hydroxy-aldehydes, hydroxy-ketones halogenated polyhydric alcohols and the like. Polyhydric alcohols that may be used for this purpose may be exemplified by glycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentaerythritol, polyallyl alcohol, polyvinyl alcohol, inositol, trimethylolpropane, bis(4-hydroxycyclohexyl)dimethylmethane and the like.

Particularly preferred members of this group com prise the glycidyl polyethers of aliphatic polyhydric alcohols containing for two to carbon atoms and having from two to six hydroxyl groups and more preferably the alkane polyols containing from two to eight carbon atoms and having from two to six hydroxyl groups. Such products, preferably have an epoxy equivalency greater than 1.0, andmore preferably, between 1.1 and 4 and a molecular weight between 300 and 1,000.

Another group of polyepoxides include the epoxy esters of polybasic acids, such as diglycidyl phthalate and diglycidyl adipate, diglycidy] tetrahydrophthalate, diglycidyl maleate, epoxidized dimethylallyl phthalate and epoxidized dicrotyl phthalate. Other suitable polyepoxides include polyglycidyl amines such as N,N- diglycidyl aniline and N,N-diglycidyl 2,4,6- tribromoaniline; low boiling polyepoxides such as diglycidyl ether, butadiene diepoxide, glycidyl glycidate and vinylcyclohexene diepoxide; and triglycidyl isocyanurate.

Examples of polyepoxides having internal epoxy groups include, among others, the epoxidized esters of polyethylenically unsaturated monocarboxylic acids, such as epoxidized linseed, ethyl 9,12-octadecadienote, and octyl 9, l 2-octadecadienoate; the epoxidized esters of unsaturated alcohols having the ethylenic group in an internal position and polycarboxylic acids such as, for example, di(2,3-epoxybutyl)adipate, di(2,3-epoxypentyl )thiodipropionate, di( 2,3-epoxybutyl )citrate and di-(4,5-epoxyoctadecyl)malonate; epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, such as 2,3-epoxybutyl 3,4-epoxypentanoate, 3,4-epoxycyclohexyl 3,4-epoxy cyclohex anoate, and 3,4-epoxycyclohexyl 4,5-epoxyoctanoate; epoxidized polymers and copolymers of diolefins such as butadiene; and bis(2,3-cpoxycyclopentyl )ether.

Polyepoxides having an epoxy cquivalent weight of between 100 and 200,000 are generally satisfactory, although polyepoxides having an epoxy equivalent weight of between about l0() and 2,000 are preferred. Particularly preferred polyepoxides are those formed from an epihalohydrin, and particularly epichlorohydrin, and a polyhydric phenol, such as 2,2- bis(4-hydroxyphenyl)propane.

The acid anhydrides employed in the process of the invention include monocyclic acid anhydrides such as succinic anhydride; bicyclic anhydrides such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic anhydride and phthalic an- 4 hydride; and polycyclic acid anhydrides such as methyl NADIC anhydride (maleic anhydride adduct of methylcyclopentadiene), chlorendic anhydrideiand alkylated endoalkylenetetrahydrophthalic anhydrides.

dipentene dimercaptan (adduct of dipentene and H 8;

marketed by Phillips Petroleum); polymercaptans such as 3,4,4'-tris(mercaptomethyl)dipentyl ether; and mercaptan-containing polysulfides prepared from sodium polysulfide and haloalkanes such as LP-8" and LP- 3 marketed by Thiokol Corporation. The amount of curing agent depends upon the number of active curing groups, e.g., mercapto or anhydride groups, present in the curing agent selected. In

general, the curable composition comprises substantially stoichiometric amounts of polyepoxide resin and curing agent, i.e., about one equivalent of epoxy group of the epoxy resin for each equivalent of curing agent,

an equivalent of curing agent being that sufficient to furnish one reactive curing group for each epoxy groups of the epoxy resin. Equivalent ratios of curing 7 agent to epoxy groups of the epoxy resin in the range of from about 0.5:l to 1:05 are satisfactory, although equivalent ratios, calculated on the same basis; from about 0.7:1 to 110.7 are preferred.

in certain modifications of the process mineral fillers, thermoplastic polymers, metal powders and level ing agents commonly used as additives in epoxy resin formulations may be included in the curable composition. Suitable additives which may be employed as desired, include among many others, aluminum powder, mica, bentonites, clays, synthetic resins and elastomers, ignited A1 0 short-fiber asbestos, wood flours, carbon black, zinc dust, talc, silicone, and the like. Preferred additives are thermoplastic polymers. By thermoplastic is meant those polymers which melt when heated, say to temperatures above 200 F. A 7

great variety of different materials are included in this group, such as, for example, polymers and copolymers of cthylenically unsaturated monomers such as ethylene, propylene, vinyl chloride, vinyl bromide,

dichlorostyrene, acrylonitrile and vinyl polyester type resins, polybasic acids such as terephthalic acid and polyhydric alcohols such as trimethylene glycol; and the polyamides such as nylon.

Of special importance are the nylons. Nylon as used herein is deemed to be the generally accepted usage of the term, i.e., the generic term for a class of polyamides containing separating amide groups (CONH connected by methylene units (CH in the polymer structure. The nylons are prepared by condensing a diamine with a dibasic acid. With the variety of acetate;

diamines and dibasic acids available, many different.

types of nylons are possible. In general, all polyamides which are customarily called nylon are suitable for 4( I-Z-dimercaptoethyl l ,Lcyclohexanedithiol,

i .c., reaction products of use in the present invention. The most common types in commercial use today are nylon 6, nylon 66 and nylon 610. These numbers represent a convenient method of designating the nylons according to the number of carbon atoms in the segments of the starting diamine and dibasic acid from which they are made. For example, nylon 66 is made from hexamethylenediamine and adipic acid, both of which contain six carbon atoms. Nylon 6 uses caprolactam, a cyclic acid amide NH(CH CO which contains six carbon atoms as its starting material. Nylon 610 is made from hexamethylene-diamine and sebasic acid which contains 10 carbon atoms.

The quantity of additive used is dependent upon many factors such as cost, particule size, particle shape, absorption characteristics and loading volume. In general, however, the additives are employed in ratios up to I50 phr (parts per one hundred parts of polyepoxide).

In certain modifications of the process, it is also desirable to incorporate into the compositions to be cured minor amounts of a chemical free radical initiator as a catalyst promoter. The use of the chemical free radical initiator promotes a cure of uniform hardness, particularly in thick films of epoxy resins. Suitable free radical initiators include organic peroxides such as dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide and tert-butyl hydroperoxide and azo compounds such as alpha,alpha-azo-bis-isobutyronitrile and alpha,alphaazo-bis-methylisobutyrate. The amount of catalyst promoters is not critical, and no catalyst promoters are required. When present, amounts of catalyst promoters up to about l0 phr (parts per one hundred parts of calculated on polyepoxide) are satisfactory.

The polyepoxide resin, curing agent, photocatalyst, additive, if any, and catalyst promoter, if any, are stirred or agitated to provide a substantially uniform liquid or solid mixture before curing. However, if the polyepoxide-containing mixture to be cured is semisolid or solid, it may be convenient to employ a solvent which is inert to the reactants to provide a liquid curable mixture. Suitable solvents include ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran and CELLOSOLVE (monoand dialkyl ethers of ethylene glycol); esters such as ethyl acetate and amyl acetate; halogenated alkanes such as methylene chloride and chloroform; and aromatic hydrocarbons such as toluene and xylene. Alternative, reactive diluents such as allyl glycidyl ether, phenyl glycidyl ether or butyl glycidyl ether may be blended with the polyepoxide-containing mixture to provide a liquid mixture.

The uncured mixtures of epoxy resin, curing agent, and photocatalyst are handled and stored in subdued light or darkness until they are to be cured. When curing is to take place, the compositions are exposed to electromagnetic radiation for an effective length of time, for example, from about 5 minutes upward to as much as 1 week. Electromagnetic radiation of wave lengths from I A to 7000 A, e.g., gamma rays, x-rays, ultraviolet and visible light, are suitable for initiating the cure. However, the ultraviolet to visible range (1500 A to 6000 A) is preferred. A commonly available radiation source which can be employed herein is direct sunlight inasmuch as the radiation of the sun contains ultraviolet light and visible light. Similarly, lamps which operate on the principle of a zinc, cadmium, thallium, gallium, indium, carbon, mercury,zir conium, hydrogen, deuterium, xenon or helium arc can likewise be employed in the exercise of' the present invention. Preferred lamps for employment in thepresent invention include those commercially available highpressure mercury arc lamps, pulsed xenon arclamps and carbon arc lamps having a total power capacity ranging from about 50 watts to about 10,000 watts, preferably from about 1000 watts to about 6000 watts. These lamps emit a broad spectrum of light including ultraviolet and visible radiation. Likewise preferred are the low-pressure mercury lamps having a total power capacity ranging from about 0.5 watt to about 50 watts. These lamps emit monochromatic light generally in wave lengths of about 253.7 m or with the addition of suitable phosphors in the regions of 300 m and 355 m for example. Other utilizable light sources are ordinary fluorescent lamps which emit in the 350 m region of the light spectrum. The lamps hereinbefore described are well known to those skilled in the art and are commercially available. These lamps are described in greater detain in Ultraviolet Radiation by L. R. Coller, 2nd edition, John Wiley & Sons, Inc. (1952), which disclosure is incorporated herein by reference.

The time required for the irradiation is generally a period of time from about 1 minute to about hours, preferably from about 10 minutes to 8 hours. The reaction time varies with the concentration of the starting material in the solvent, the nature of the solvent, the intensity of the irradiation source, the physical reaction conditions, the temperature of reaction and the adsorption of the irradiation by the reaction vessel. However, the course of the reaction can readily be followed by conventional techniques, e.g., by determining the hardness of the cured composition.

Exposure to radiation for an effective length of time at substantially room temperature (25 C) produces a cure that is dry to the touch. However, the composition is optionally heated at a temperature ranging from 50 C to 250 C for about l hour to 3 days to accelerate and complete the cure. When acid anhydrides are employed as the curing agents, the cure is preferably completed by heating. The heat treatment is carried out separately or is carried on substantially simultaneously with the exposure to radiation,

Applications for the invention are in light sensitive printing plates, stamping tools, adhesives, decoration of metal, wood or plastic surfaces, preparing a perforated plastic sheet or fine mesh screen, photoresists for electronic circuits, chemical milling, holographic recording film, lithography, foamed-in-placc resins, preparation of heat-shrinkable poly-vinylchloride or nylon film, in cures at locations remote from a resin mixing pot but accessible to light, e.g., in oil wells.

Light-induced epoxy resin cures are particularly suitable for surface coatings, for example, as by applying a solution of the epoxy resin, curing agent and 'photocatalyst to a surface and exposing the coated surface to radiation. In certain instances, it might be desirable to shield various parts of the surface before exposing it to radiation. This is accomplished by masking predetermined portions of the surface with a layer of material having substantial opacity to prevent radiation from reaching the surface areas not requiring polymerization. To accomplish such masking, for ex- In the dark, the above resin mixture has a pot life of several weeks.

EXAMPLE I] amp Shielding, -g-. a Stencil, is Placed p of the A cotton cloth was painted with a mixture Containing surface. The radiation will penetrate the clear areas 32,5 percent wt EPQN Resin 1004, 6.5 percent wt and cause polymerization. The opaque areas will block methyl NADIC anhydride, 1 percent wt methylthe radiation. After the exposure to radiation has been cyclopentadienylmanganese tricarbonyl and 60 percompleted, the Shielding, if y, is removed n the centwttetrahydrofuran. The painted cloth was allowed surface soaked in a solvent such a chlorinated solvent to d i ht. Th l th was covered with a stencil, r a k t 10 r m the np lym rize Coating irradiated with a water-cooled, high-pressure mercury ture from the shielded areas of the surface. After the are lamp (General Electric AH-6) for 56 hours from a soaking, the polymerization process is completed and distance of 30 cm, and then baked at 125 C for 2.5 the Surfacels for hours in a ventilated oven. The cloth was soaked in 0Xygen is a free-radical scavenger and generally methyl ethyl ketone to remove the unexposed (unfree-radical initiated polymerizations must be concured) resin A Sharp image f cured resin ducted in the absence of Oxygen or An advantage of responding to the image of the stencil) remained in the the curing process of the invention is that is can be conl th. ducted in the presence of an oxygen-containing at- EXAMPLE I" mosphere. This advantage is of particular importance I in surface coating applications wherein the epoxy com- A r g icontammg mfnor position to be cured is most conveniently applied in the amoun 0 me y cyc oPema manganese tricarbonyl catalyst were applied to a tinplate surface and open atmosphere. 2S

cured by exposure to a General Electric AH-(i lamp. X The resin mixture components, the film thickness, the irradiation time, the drying time (time at which film This example illustrates the preparation of a printing becomes dry to touch) and the pot life (time at which P unexposed film becomes dry to the touch) are provided A tinplate panel was doctored at (3 with a two in Table i. In the Table, A designated EPON Resin mil coating of a mixture containing 81.5 percent wt 826, (glycidyl polyether of Bisphenol A having an EPON 1004 Resin (Bisphenol A) diglycidyl ether resin average epoxide equivalent weight of about 175-190 having an epoxy equivalent weight of 875-1025 and an n n average molecular weight of about average molecular weight of about 1400), 16.0 percent deslgnates EPON Resin 815 y y P l/ of wt methyl NADlC anhydride [methy]bicyc|o(2 Bisphenol A having an average molecular weight of 2.1 )heptene-2,3-dicarboxylic and and 2.5 percent wt about an Fpoxlde eqmvaien? weight of methylcyclopentadienyl-manganese tricarbonyl. The 175 C deslgnates EPON ReSm 154 (a glycldyl polyether prepared by condensing a phenol-formalpanel was covered with a stencil, irradiated for A hour 4O dehyde novolak with epichlorohydrin and having an at room temperature with a water-cooled, high-pres- I. (General Electric AH 6) from a epoxide equivalent weight of 176-181). D designates sure meltcuryarc o I EPON Resin 1001 (solid condensate of Bisphenol A 30 cm distance and then baked at 125 for 2 hours in and epichorohydrin having an average molecular a ventilated oven. The panel was soaked in methyl ethyl weight of about 900 and an epoxide equivaigm weight ketone and rubbed with steel wool to remove the unexf 450 550) 13" designates EPONOL Resin 4 Posed (uncured) resin Produce the image of the (solid condensate of Bisphenol A and epichlorohydrin stencil. Cured areas were unaffected by the methyl having an epoxide equivalent weight of about ethyl ketone or steel wool treatments. 200,000). The resin mixture of Run 16 contains 0.16 g

TABLE 1 Film Irmill- Drying Catal-lilukiitloii tliiin, Pol. lll'u, I lyst, 11035, Mimi, (lays in; days Epoxy resin, g. Curing agent, g. g. Solvent, 5:. nills hrs 25 C.

E, 5.0 None 0.07 Cellosolve, 1.0 10-30 3 50 50 E, 1.29..- Hexanetriol trithioglycolate, 0.9.. 0.07 None 10 7 12 E, 5.0.-.. Hexanetriol trithioglycolate, 3.48. 0. 12 Dimethoxyethano, 3.3 10-30 3 1 24 E, 2.2 Hexanetriol trithioglycolate, 1.59 0.13 Dimethoxyethane, 1.0 5 3 0,5 7 E, 4.63... Tr1(mercaptoniethy1) diphenyl ether, 2.72.. 0. 25 Dimethoxyethane, 2.8. 5 3 0,1 7 E, 3.70... Tri(mereaptomethy1) diphenyl other, 2.18.- 0. 20 Dlmethoxyethane, 3.0 5 3 0. 1 7 E, 6.0-... Tri(mercaptomethy1) diphenyl other, 1.1 0.21 Dimethoxyethano, 3.1 5 3 0. 1 7 E,1.8- Dipsnteriedimercaptan,0.14 0.14 None... 10 1,7 2 12 E, 3.6.... Dipontenedimercaptan, 2.0-.-. 0. 1 Cellosolvo, 4 4..- 5-10 3 0, 5 11 E,3.6 o 0.10 Butanol, 2 2.. 5-10 3 0,5 20 E,3.70 Pentaerythritol-tetrathioglycolate, 2.3 0. 30 None 10 1 E,3.70 o 0.80 o 10 1 E 2.0 Dodecylsucoinic anhydride 2 4 0.24 Dlmothoxyethane, 1 10 3 11 36 E, 5.0 Methyl nadie anhydride, 4 0.135 Dimethoxyethane, 3 10-30 3 12 25 E, 2.0.. Methyl nadic anhydride 1 0. 20 Dimethoxyethane, 1 10 3 1 22 E,2.0-. ...do 0.20 ...--do 10 3 11 25 E, 7.0 olysulfide, 12.0-. 0. 51 None 10 0. 25 1 10 E, 1.0 Methyl nadlc anhydride, 1.0. 0.25 Methyl ethyl kotone, 12.5. 10 0.25 (B) E, 2.0 Methyl nadir: anhydride, 2.0- 0. 5 Methanol, 00 10 0.25 (1 100 E 1.0.. ---..do 0.25 Tetrahydroiuran, 45.. 10 0. 25 100 E .1 Polysulfida, 6.0 0.4 None 2 0.25 1 l0 s 5 minutes. b 6 minutes. it 2 hours, C.

1 claim as my invention:

1. A composition of matter comprising, in admixture, (1) a polyepoxide resin having an epoxy eduivalency greater than one, (2) a curing agent selected from monocyclic and polycyclic acid anhydrides and polymercaptans containing more than one mercapto group, the equivalent ratio of curing agent to epoxy groups of the polyepoxide resin being in the range of from about 0.5:1 to 1:05, and (3) a catalytic amount of a cyclopentadienylmanganese tricarbonyl, said composition having had substantially no exposure to electromagnetic radiation.

2. The composition of claim 1 wherein the polyepoxide resin is a glycidyl polyether of a polyhydric phenol and the curing agent is an aliphatic polycyclic acid anhydride.

3 The composition of claim 2 wherein the curing' agent is methylbicyclo(2.2.1 )heptane-2,S-dicarboxylic acid anhydride and the cyclopentadienylmanganese tricarbonyl compound is methylcyclopentadienylmanganese tricarbonyl. 

2. The composition of claim 1 wherein the polyepoxide resin is a glycidyl polyether of a polyhydric phenol and the curing agent is an aliphatic polycyclic acid anhydride.
 3. The composition of claim 2 wherein the curing agent is methylbicyclo(2.2.1)heptane-2,3-dicarboxylic acid anhydride and the cyclopentadienylmanganese tricarbonyl compound is methylcyclopentadienylmanganese tricarbonyl. 